CN102250326A - Technology for preparing polybutylene terephthalate (PBT) by using phenylene terephthalamide (PTA) residues as raw material - Google Patents
Technology for preparing polybutylene terephthalate (PBT) by using phenylene terephthalamide (PTA) residues as raw material Download PDFInfo
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- CN102250326A CN102250326A CN201110156485XA CN201110156485A CN102250326A CN 102250326 A CN102250326 A CN 102250326A CN 201110156485X A CN201110156485X A CN 201110156485XA CN 201110156485 A CN201110156485 A CN 201110156485A CN 102250326 A CN102250326 A CN 102250326A
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Abstract
The invention discloses a technology for preparing polybutylene terephthalate (PBT) by using phenylene terephthalamide (PTA) residues as raw materials. The technology comprises the following steps: treating PTA-containing residues, then adding methanol and a catalyst to perform a secondary esterification reaction, performing separation and reduced pressure distillation to obtain the finished product dimethyltryptamine (DMT), then adding 1,4-butanediol and the catalyst to perform an alcoholysis reaction and a polymerization reaction, finally injecting nitrogen, granulating, cooling and sieving to obtain the product. The technology has low cost and high added value and esterification rate; the demands on equipment are reduced, the equipment can not be corroded basically, the recycling of the waste can be realized, the maximum recycling of the waste can be realized, and the resource consumption for refining PTA can be reduced; and the environmental protection problem of the enterprise is solved, the sustainable development of the enterprise can be realized and the enterprise has competitive advantages.
Description
Technical field
The present invention relates to the manufacturing process of a kind of PBT, especially relating to a kind of is the technology that raw material is made PBT with the PTA residue.
Background technology
PBT, full name is poly terephthalic acid 1,4 butanediol esters or polybutene are to dicarboxylic acid esters, by 1,4 butyleneglycols and terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) are polymerized, and the translucent or opaque crystalline thermoplastic polyester's resin of making via mixing program of oyster white.Because PBT resin-CH2-chainpropagation makes molecular chain be easy to deflection, so the vitrifying tansition temperature is lower than polyethylene terephthalate (PET), curing speed is fast.PBT is a kind of crystallinity, high molecular weight polymers, has the good rerum natura and the balance of processing characteristics.Because the crystallization velocity of material is quick, make that the cycling time of moulding is short, and mold temperature is lower than a lot of engineering plastics, its density is between 1.31-1.55, fusing point is at 224-230 ℃, and the life-time service temperature can reach more than 120 ℃, because of it has excellent characteristic, be widely used in industry such as electronics, electrical equipment, communication cable, automobile, market outlook are wide.
PBT produces and mainly to concentrate on states such as America and Europe, Japan and Korea S, and China is based on import, and domestic production strength is not enough, and the price height.Existing company all is that the PAT with exquisiteness is that raw material is made PBT, production cost height like this, and added value is low, and is difficult to bear the impact of import market, can't satisfy the demand of existing market.For this reason, need technical renovation in a hurry, reduce production costs, improve the production output and the market competitiveness.
In addition, since the reform and opening-up, the China's oil chemical engineering industry is developed on an unprecedented scale, and numerous light textile enterprises and printing and dyeing mill are raw material with PTA, produces many PTA residue pollutents for this reason, and the CDO value that contains simultaneously increases, and the influence discharging seriously restricts the development of industry; The directly discharging if do not handle, this causes significant stress to environmental protection, brings for simultaneously enterprise and peripheral environment and has a strong impact on, and hinders Sustainable Development of Enterprises., need recycle for this reason, especially be used for producing PBT the PTA residue, there is deficiency in prior art, and is high for the erosion resistance requirement of production unit, but esterification yield is not high, make production cost improve, by product increases, and complex procedures and recovery are difficult for.This shows that addressing the above problem is extremely urgent.
In view of this, the inventor has done deep research to this, by feat of the experience of being engaged in relevant industries for many years and practice, designing a kind of is the technology that raw material is made PBT with the PTA residue, and cost is low, the added value height, the esterification yield height reduces and does not have corrosion, realization regenerated resource development and utilization substantially for equipment requirements, and make its refuse maximum resourceization, reduce refining PTA resource consumption, solve the environmental protection of enterprise problem simultaneously, make Sustainable Development of Enterprises, have competitive edge, this case produces thus.
Summary of the invention
The object of the present invention is to provide a kind of is the technology that raw material is made PBT with the PTA residue, cost is low, the added value height, the esterification yield height reduces and does not have corrosion substantially for equipment requirements, realize regenerated resource development and utilization, and make its refuse maximum resourceization, and reduce refining PTA resource consumption, solve the environmental protection of enterprise problem simultaneously, make and Sustainable Development of Enterprises have competitive edge.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of is the technology that raw material is made PBT with the PTA residue, it is characterized in that may further comprise the steps:
The first step is handled the residue that contains PTA: carry out expansion drying earlier, then pulverization process;
Second step, the secondary esterification:
Esterification for the first time: after pulverization process, adding is according to the methyl alcohol of mol ratio 1: 12-14 with according to the catalyzer of total mass ratio 2 ‰-4 ‰, this moment, temperature of reaction was: 100 ℃-150 ℃, reaction times is 4-6h, behind the molecular balance, carry out the dealcoholysis processed, obtain DMT (A) and recovery and obtain methyl alcohol;
Esterification for the second time: among DMT (A), add with step 3 in the methyl alcohol of amount, stir behind the reaction terminating and cool off, carry out solid-liquid separation with the closed whizzer, obtain DMT (B), and DMT (B) mother liquor reclaimed the methyl alcohol that obtains;
In the 3rd step, DMT (B) rectification under vacuum is obtained finished product DMT;
The 4th step, alcoholysis reaction: in finished product DMT, add according to 1,4 butyleneglycol of mass ratio 10%-40% with according to the titanic acid ester of total mass ratio 2 ‰-4 ‰, obtain terephthalic acid 1,4 butanediol ester monomer;
In the 5th step, polyreaction: after filtering earlier, then entering in the polymeric kettle, is to react under 230 ℃-280 ℃ in vacuum condition, temperature, and polycondensation becomes PBT, and reclaims 1,4 excessive butyleneglycol;
In the 6th step, finish product: charge into nitrogen earlier, carry out granulation through tablets press, then cooling, sub-sieve are packed, and finish product.
Further, the catalyzer in described second step is a vitriol:
Further, described vitriol is bodied ferric sulfate or titanium sulfate;
Used catalyzer in the technology among the present invention, catalytic efficiency height not only, and do not have the three wastes to produce substantially, help the protection of environment; Simultaneously, the consumption of methyl alcohol has also reduced, and saves production cost.In process of production, reduce corrosion widely, prolong the work-ing life of equipment, obtain the certain economic effect, help market competition advantage production unit.
Beneficial effect of the present invention: because the present invention is to be that raw material is made PBT with the PTA residue, so technology cost of the present invention is low, the added value height, the esterification yield height reduces and does not have corrosion substantially for equipment requirements, realize regenerated resource development and utilization, and make its refuse maximum resourceization, and reduce refining PTA resource consumption, solve the environmental protection of enterprise problem simultaneously, make and Sustainable Development of Enterprises have competitive edge.
In order further to explain technical scheme of the present invention, the present invention will be described in detail below by specific embodiment.
Embodiment
The present invention relates to a kind of is the technology that raw material is made PBT with the PTA residue, and it may further comprise the steps:
The first step is handled the residue that contains PTA: carry out expansion drying earlier, then pulverization process; In this step, the contained moisture of the residue behind expansion drying is at 1%-8%, and the residue after pulverization process helps carrying out esterification like this less than 20 orders, and reaction more fully and fast, makes esterification yield higher;
Second step, the secondary esterification:
Esterification for the first time: after pulverization process, adding is according to the methyl alcohol of mol ratio 1: 12-14 with according to the catalyzer of total mass ratio 2 ‰-4 ‰, this moment, temperature of reaction was: 100 ℃-150 ℃, reaction times is 4-6h, behind the molecular balance, carry out the dealcoholysis processed, obtain DMT (A) and recovery and obtain methyl alcohol;
This for the first time in the esterification, adds the amount of methyl alcohol, is according to the mol ratio that contains PTA residue and methyl alcohol after pulverization process, promptly 1: 12-14 adds, because significantly reduce through contained humidity behind the expansion drying, becomes solid, powdery, be difficult for flowing, so need to add the methyl alcohol of this tittle; Another side is in order to react more abundant complete.In first time esterification, the esterification yield of PTA reaches 70%; After the reaction, need carry out the dealcoholysis dehydration and reclaim methyl alcohol, reduce production costs, the realization resource is recycled;
Catalyzer in this step is selected vitriol for use, generally selects bodied ferric sulfate or titanium sulfate for use, adds the amount of catalyzer, is to contain 2 ‰-4 ‰ of PTA residue and methyl alcohol total mass after pulverization process; This catalyst efficiency height, and the three wastes that produced significantly reduce, and help the protection of environment; Simultaneously, the consumption of methyl alcohol has also reduced, and saves production cost.In process of production, reduce corrosion widely, prolong the work-ing life of equipment, obtain the certain economic effect, help market competition advantage production unit.
Esterification for the second time: among DMT (A), add with step 3 in the methyl alcohol of amount, stir behind the reaction terminating and cool off, carry out solid-liquid separation with the closed whizzer, obtain DMT (B), and DMT (B) mother liquor reclaimed the methyl alcohol that obtains;
In second time esterification, add with esterification for the first time in the methyl alcohol of amount, after through the dealcoholysis dehydration, catalyzer is still stayed the inside, so need not add catalyzer in the esterification in the second time.In second time esterification, the esterification yield of PTA reaches more than 98%;
Process of cooling need reduce the temperature to below 30 degree, helps centrifugation, this closed whizzer help stoping methyl alcohol and volatilization.
In the 3rd step, after cooling, DMT (B) rectification under vacuum is obtained finished product DMT;
Rectification under vacuum during this step is cold is a prior art;
The 4th step, alcoholysis reaction: in finished product DMT, add, obtain terephthalic acid 1,4 butanediol ester monomer according to 1,4 butyleneglycol of mass ratio 10%-40% with according to the titanic acid ester of total mass ratio 2 ‰-4 ‰;
In the 4th step alcoholysis reaction, 1, the amount that 4 butyleneglycols add is the 10%-40% of finished product DMT quality, titanic acid ester adds as catalyzer, its amount is 2 ‰-4 ‰ of 1,4 butyleneglycol and a finished product DMT total mass, in such ratio, terephthalic acid 1, the 4 butanediol ester monomer that reaction obtains is best.
In the 5th step, polyreaction: after filtering earlier, then entering in the polymeric kettle, is to react under 230 ℃-280 ℃ in vacuum condition, temperature, and polycondensation becomes PBT, and reclaims 1,4 excessive butyleneglycol;
In the 6th step, finish product: charge into nitrogen earlier, carry out granulation through tablets press, then cooling, sub-sieve are packed, and finish product.
Embodiment one
A kind of is the technology that raw material is made PBT with the PTA residue, may further comprise the steps:
The first step is handled the residue that contains PTA: carry out expansion drying earlier, then pulverization process;
Second step, the secondary esterification:
Esterification for the first time: after pulverization process, add according to 1: 12 methyl alcohol of mol ratio with according to the catalyzer of total mass ratio 2 ‰, this moment, temperature of reaction was: 150 ℃, reaction times is 4h, behind the molecular balance, carry out the dealcoholysis processed, obtain DMT (A) and recovery and obtain methyl alcohol;
Esterification for the second time: among DMT (A), add with step 3 in the methyl alcohol of measuring, stir behind the reaction terminating and be cooled to temperature and be lower than 30 degree, carry out solid-liquid separation, obtain DMT (B) with the closed whizzer, and DMT (B) mother liquor reclaimed the methyl alcohol that obtains;
In the 3rd step, DMT (B) rectification under vacuum is obtained finished product DMT;
The 4th step, alcoholysis reaction: in finished product DMT, add according to 1,4 butyleneglycol of mass ratio 40% with according to the titanic acid ester of total mass ratio 2 ‰, obtain terephthalic acid 1,4 butanediol ester monomer;
In the 5th step, polyreaction: after filtering earlier, then entering in the polymeric kettle, is to react under 280 ℃ in vacuum condition, temperature, and polycondensation becomes PBT, and reclaims 1,4 excessive butyleneglycol;
In the 6th step, finish product: charge into nitrogen earlier, carry out granulation through tablets press, then cooling, sub-sieve are packed, and finish product.
Embodiment two
A kind of is the technology that raw material is made PBT with the PTA residue, may further comprise the steps:
The first step is handled the residue that contains PTA: carry out expansion drying earlier, then pulverization process;
Second step, the secondary esterification:
Esterification for the first time: after pulverization process, add according to 1: 13 methyl alcohol of mol ratio with according to the catalyzer of total mass ratio 2.5 ‰, this moment, temperature of reaction was: 120 ℃, reaction times is 4h, behind the molecular balance, carry out the dealcoholysis processed, obtain DMT (A) and recovery and obtain methyl alcohol;
Esterification for the second time: among DMT (A), add with step 3 in the methyl alcohol of measuring, stir behind the reaction terminating and be cooled to temperature and be lower than 30 degree, carry out solid-liquid separation, obtain DMT (B) with the closed whizzer, and DMT (B) mother liquor reclaimed the methyl alcohol that obtains;
In the 3rd step, DMT (B) rectification under vacuum is obtained finished product DMT;
The 4th step, alcoholysis reaction: in finished product DMT, add according to 1,4 butyleneglycol of mass ratio 30% with according to the titanic acid ester of total mass ratio 2.5 ‰, obtain terephthalic acid 1,4 butanediol ester monomer;
In the 5th step, polyreaction: after filtering earlier, then entering in the polymeric kettle, is to react under 230 ℃ in vacuum condition, temperature, and polycondensation becomes PBT, and reclaims 1,4 excessive butyleneglycol;
In the 6th step, finish product: charge into nitrogen earlier, carry out granulation through tablets press, then cooling, sub-sieve are packed, and finish product.
Embodiment three
A kind of is the technology that raw material is made PBT with the PTA residue, may further comprise the steps:
The first step is handled the residue that contains PTA: carry out expansion drying earlier, then pulverization process;
Second step, the secondary esterification:
Esterification for the first time: after pulverization process, add according to 1: 13.5 methyl alcohol of mol ratio with according to the catalyzer of total mass ratio 3 ‰, this moment, temperature of reaction was: 100 ℃, reaction times is 6h, behind the molecular balance, carry out the dealcoholysis processed, obtain DMT (A) and recovery and obtain methyl alcohol;
Esterification for the second time: among DMT (A), add with step 3 in the methyl alcohol of measuring, stir behind the reaction terminating and be cooled to temperature and be lower than 30 degree, carry out solid-liquid separation, obtain DMT (B) with the closed whizzer, and DMT (B) mother liquor reclaimed the methyl alcohol that obtains;
In the 3rd step, DMT (B) rectification under vacuum is obtained finished product DMT;
The 4th step, alcoholysis reaction: in finished product DMT, add according to 1,4 butyleneglycol of mass ratio 10% with according to the titanic acid ester of total mass ratio 4 ‰, obtain terephthalic acid 1,4 butanediol ester monomer;
In the 5th step, polyreaction: after filtering earlier, then entering in the polymeric kettle, is to react under 250 ℃ in vacuum condition, temperature, and polycondensation becomes PBT, and reclaims 1,4 excessive butyleneglycol;
In the 6th step, finish product: charge into nitrogen earlier, carry out granulation through tablets press, then cooling, sub-sieve are packed, and finish product.
Embodiment four
A kind of is the technology that raw material is made PBT with the PTA residue, may further comprise the steps:
The first step is handled the residue that contains PTA: carry out expansion drying earlier, then pulverization process;
Second step, the secondary esterification:
Esterification for the first time: after pulverization process, add according to 1: 14 methyl alcohol of mol ratio with according to the catalyzer of total mass ratio 4 ‰, this moment, temperature of reaction was: 135 ℃, reaction times is 5h, behind the molecular balance, carry out the dealcoholysis processed, obtain DMT (A) and recovery and obtain methyl alcohol;
Esterification for the second time: among DMT (A), add with step 3 in the methyl alcohol of measuring, stir behind the reaction terminating and be cooled to temperature and be lower than 30 degree, carry out solid-liquid separation, obtain DMT (B) with the closed whizzer, and DMT (B) mother liquor reclaimed the methyl alcohol that obtains;
In the 3rd step, DMT (B) rectification under vacuum is obtained finished product DMT;
The 4th step, alcoholysis reaction: in finished product DMT, add according to 1,4 butyleneglycol of mass ratio 20% with according to the titanic acid ester of total mass ratio 3 ‰, obtain terephthalic acid 1,4 butanediol ester monomer;
In the 5th step, polyreaction: after filtering earlier, then entering in the polymeric kettle, is to react under 270 ℃ in vacuum condition, temperature, and polycondensation becomes PBT, and reclaims 1,4 excessive butyleneglycol;
In the 6th step, finish product: charge into nitrogen earlier, carry out granulation through tablets press, then cooling, sub-sieve are packed, and finish product.
As from the foregoing, the present invention is to be that raw material is made PBT with the PTA residue, so technology cost of the present invention is low, the added value height is realized regenerated resource development and utilization, and is made its refuse maximum resourceization, reduce refining PTA resource consumption, solve the environmental protection of enterprise problem simultaneously, make Sustainable Development of Enterprises to have competitive edge.Because catalyzer is elected titanium sulfate and bodied ferric sulfate as, not only catalytic efficiency height, such requirement that has just reduced the equipment erosion resistance, the work-ing life and the production unit cost of prolongation equipment help competitive edge.
The above is embodiments of the invention only, is not the restriction to this case design, and all equivalent variations of doing according to the design key of this case all fall into the protection domain of this case.
Claims (3)
1. one kind is the technology that raw material is made PBT with the PTA residue, it is characterized in that may further comprise the steps:
The first step is handled the residue that contains PTA: carry out expansion drying earlier, then pulverization process;
Second step, the secondary esterification:
Esterification for the first time: after pulverization process, adding is according to the methyl alcohol of mol ratio 1: 12-14 with according to the catalyzer of total mass ratio 2 ‰-4 ‰, this moment, temperature of reaction was: 100 ℃-150 ℃, reaction times is 4-6h, behind the molecular balance, carry out the dealcoholysis processed, obtain DMT (A) and recovery and obtain methyl alcohol;
Esterification for the second time: among DMT (A), add with step 3 in the methyl alcohol of amount, stir behind the reaction terminating and cool off, carry out solid-liquid separation with the closed whizzer, obtain DMT (B), and DMT (B) mother liquor reclaimed the methyl alcohol that obtains;
In the 3rd step, DMT (B) rectification under vacuum is obtained finished product DMT;
The 4th step, alcoholysis reaction: in finished product DMT, add according to 1,4 butyleneglycol of mass ratio 10%-40% with according to the titanic acid ester of total mass ratio 2 ‰-4 ‰, obtain terephthalic acid 1,4 butanediol ester monomer;
In the 5th step, polyreaction: after filtering earlier, then entering in the polymeric kettle, is to react under 230 ℃-280 ℃ in vacuum condition, temperature, and polycondensation becomes PBT, and reclaims 1,4 excessive butyleneglycol;
In the 6th step, finish product: charge into nitrogen earlier, carry out granulation through tablets press, then cooling, sub-sieve are packed, and finish product.
According to claim 1 described a kind of be the technology that raw material is made PBT with the PTA residue, it is characterized in that: described second the step in catalyzer be vitriol.
According to claim 2 described a kind of be the technology that raw material is made PBT with the PTA residue, it is characterized in that: described vitriol is bodied ferric sulfate or titanium sulfate.
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| CN201110156485XA CN102250326A (en) | 2011-06-10 | 2011-06-10 | Technology for preparing polybutylene terephthalate (PBT) by using phenylene terephthalamide (PTA) residues as raw material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017022A (en) * | 2015-07-20 | 2015-11-04 | 浙江大学 | Method for methyl esterification recovery and recycle of PTA oxidation residue |
| CN109651139A (en) * | 2018-12-11 | 2019-04-19 | 南京科技职业学院 | The method and device system of secondary white clay synthesis DOTP |
| CN113549200A (en) * | 2021-07-15 | 2021-10-26 | 江苏志成新材料科技有限公司 | Process method for chemically regenerating degradable polyester by using PBT polyester |
-
2011
- 2011-06-10 CN CN201110156485XA patent/CN102250326A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017022A (en) * | 2015-07-20 | 2015-11-04 | 浙江大学 | Method for methyl esterification recovery and recycle of PTA oxidation residue |
| CN109651139A (en) * | 2018-12-11 | 2019-04-19 | 南京科技职业学院 | The method and device system of secondary white clay synthesis DOTP |
| CN113549200A (en) * | 2021-07-15 | 2021-10-26 | 江苏志成新材料科技有限公司 | Process method for chemically regenerating degradable polyester by using PBT polyester |
| CN113549200B (en) * | 2021-07-15 | 2023-05-16 | 江苏志成新材料科技有限公司 | Process method for chemically regenerating PBT polyester into degradable polyester |
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Application publication date: 20111123 |